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    4 Voltammetry

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    Daniel Camilo Cano

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    © All Rights Reserved
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    of 37
    VOLTAMMETRY Votanmetry comprise» soup of lsronayicsl methods is which formation bout he alte rte rom the measurement of arent tr tuoi of applied potent under eondleat hat seearags Paes ‘zalovor an indiatr_o working, elettode To ring about poaizatin, wa tammere working sectode has a surface fe inthe renge Between ew square millimeters and afew square mierometers. letodes with fuch smal sens re caled microelectrodes ‘At the cst, is wort to pont ot the Basi dieencs be tween vliammery an he wo pes of lestrotemial mcthodsthat we have dicuned in caret chapters. Voltimmetn raced ucon the mes surement oa cument tht develops ina clecrochemeaselLundeccon Sins of eomblete concentration polaron. In contest, potenomele Fe meisuemens ae aade a currents ta approach zero and where Bolton absent Voltammetry difers rm euloety in hat with the later steps ae taken fo minimize or compensate for heels of oncetration polarization. Furthermore, invokammatry «minimal con- on faa takes lee, whereas icone Eel a of ihe analy is converted to another tate. ‘History, the fed of volammetry developed from polarography which was discovered by the Czechoslovakian chemist farsi He}: rovsky in the early 1920s" Polvorephy fers trom other iypes of ‘oltammey in tha the working ieroeecroe takes the form of drop- ing mercury elecrode OME}. The consrition and viguepropertes ‘fhe setae so sscassed in er sxtion, ‘Voltanmetry i widey used by iorgame, physical. and bill chemist for fundamental tds of oidton and redcton process. ‘anous media, adsorption processes ov surfaces, and ekeiton taster ne ‘hemicaly modified lect sirfoces. At ooe tine, voltammetry (particular classical polarography) was an important (oa ‘ed by chemi for th etermiaton of organs ons and cern o tine apeies in ausoun slston. Inthe late 1950 a erly 16 Fowever these analyte applications were agly supplanted by various an 472 Chapter 19. Votiammety spectroscopic methods, and voltammetry eset be important in aaly- Sis except for certain special applications such asthe determination of ‘moccular oxygen in solutions the mil 9805, several major modifcations of classical votammetic techniques were developed that enhance signitanty the seastity and “lctiviy ofthe method. AL abo the sme time, he advent of -oat ‘operational tmpiiers mide possible te commer! Jevelopan fea {ely inexpensive insirumens that incorporated many of hese modifies irs and mae them avaable to chemists. The result has ben a recent resurgence of interest in applying vole methods othe deterinar tir of hos of species, particularly those of pharmaccutal intrest? Futhermore, voltammetry coufled with highperlrmance ligld eto- tmalgrphy (HPLC, Chapler 28) fas become a powerful ool (Ocike “Thalys of complex mstures of varios kinds, Moder voRammsry also ovinves to be a potent ool sed by various kins of chemists interested in-gudying oxidation and reduction processes as wells alsorption pro 194 EXCITATION SIGNALS IN VOLTAMMETAY In volammetry.a variable potcaialexciation signal is inpresed! upon _aneletrochemial call containing microelectrode. This ciation signal ‘lcs a tharacterstccurtent response upon which the method fs based. “The waveforms a tree ofthe most common excitation signals used i voltammetry are shown in Figure 19 The classical voltmmetric exc tion signal se linear sean shown in Figure T9-La, a which the de ‘poenial applied to the cll increases local (usually over 23.193. Fangs) as function of tine. The current that develops nthe ellis then ‘recorded 2 Tanction of time (and thus a 2 function of the applied potenti. "Two puls-ype excitation signals are shown in Figues 19-Ib and “Thelast column n Figure 19 lists the types ofvollammery that employ the various exciton signals. These technaques are dscused in the see ons that flow 198 LINEAR-SCAN VOLTAMMETRY “The ealiest and simplest volumetric methods were of the lnearscan type. i which the potential of the working electrade is oeresed ot sereaed at atypical ate of? to $ Vis. The euren, usually in ero lampers, i then recorded to gite a vltammogram, which pol of ‘urrentas function of potential spied tothe working letrode Linea Sean vdlammetry so 80 types hydrodyn and sarap 196 tinwaeScan Votammety 478 Peet sates ese on ene om. Pi =, om semeee 198-1 Vottammetric Systems Figure 19-2 a schematic showing the components ofan apparatus for ‘arrying out votanmetrc measurements, The parts is sist tat shown n Figure 18-8. Thecllis made up of thee lecroces immerse in 1 solution containing the analyte and alo an exces ofa nonreactive Figure 1904 ei itn pe gure 19-2 Ain J 4 Chapter 9 Votemmety electrolyte called a supporting elec, One he thre electro is ‘be microtetode, or working eEctrode, whose potent controled at 1 hxed known valve or as In the case of linecracan voltammetry, fs “arid fncarty wih tie. s dimensions are Ket small inorder to 2° ance it tendency to became polanze. The second electrode rer ‘ore BOER Fema onsan oughou he eapet- iment. Tho tid eocteod is counter elerode which soften 9 of platinum wre or pool of merry tha simpy serves to conduct current from the source through te solton to the misrstectrode. The sina source is arabe de power supply consisting oa batey in seis with ‘arabe resistor. The desited potenal i eected by moving the onact Ct the proper postin on he resto. The elect! resistance ‘the cet containing the reference secre bs lrge © 10") at sently no currents present in Thus, the eae erent from the ‘Surce is caved fr te counter cketrode tote micoeetrode. A ‘ollammogram i recorded by moving th conat Cin Figre 19-2 and ‘ecoring the resulting current a anton ofthe potential between the Working lecode and the reference electrode Tm rien. the manalpotentotat of Figure 1-2 could be used to erate alinearscn voltammogram. In such at experiment contact © oul be moved ata constant rate from Ato Bt produce the exctation nal shown in Figure 1D-la The cent and volge would then be recorded a conseutive eal time intervals daring the voltage (0 ine) Sean. Unforunatly tifa to mainain acomstant eof mation of the siding contact sd equally eifet to recor he curent mana ‘Thus, in practice we would record a mana votammesram 8y moving onc Cin small ierement inated by he dg voltmeter n Figure 19-2, For each increment of volge, the resukig cument would ber corded to produce vallammogzam point by pm. Is Important to Emphasize thatthe independent vara inthis experiments the poten. {al ofthe microetecrrde versus the reference cetrode a noth po- teal between the microelectrode andthe coun electro, ‘The eeu of Fire 19-2 functions qe cel for recording cent ats fed polenta or for generating manual volummograms However, omples excitation signals suchas those shown in Figure 19-Ib and & tmustbe penerated elecvoncaly. Moder volanmeiric instruments aloe matically vay the potential in preseribed way oth respec othe reer ‘nce clccroge and record the relingcuren poentostat based on ‘operational amples that designed Yo cary ou is tasks deseibedin Feature 19-1 198-2 microelectrodes “The microelectrodes employe in voltammetry lake a vary of shapes and forms. Oftea, they ae small at dsks of «conductor tat are pres. fitted into rod ofan inert materi suchas Teflon or Kel, hat has 8 ire contact imbedded in it (See Figure 19-5), The conductor maybe an Ine maa. ich ptm egal; protic papi o ary etons & Semiconductor, suchas tin or ndium oxide; ors metal coated with afm 198 UnesrScan Votammety 475 rs Festure 19-1 VOLTAMMETRIC INSTRUMENTS BASED ON OPERATIONAL AMPLIFIERS In Fenture 17-2 we describe the use of operational amples to measure the potential of electrochemical eal. Op amps aso can be ‘sed to measure currents and carry out varity of ober conta, and measurement asks. Let us consider the measremeat of cur ena lustrated in Figure 19-2, Tn this circuit volage source Is asched to one electrode of an clecrochemical cell, which produces a current! the eal. Be- cause of the very high input resistance ofthe opamp, esenialy tlle the eurzet pasts through the resistor Rt the output ofthe ‘op amp. The voltage athe output ofthe op amp is ven by Ohm's Iaw Enz =~ 7. By slving this equation for we ave By t= Fo ice tee ieren te eedesrial et ep tones eng aupal opamp tisvuce fcc | ian Suediscucied dagen | Saisie ec scree taco meee oe, pots npaed gee has oa het ees eee al (ara hea op enp) Me ets ec abe | Cette adore opcee buns case ns eae | Toit ietoes momen te potavel be ese: cero | ea nearer canal gia see BION Petes sates mach ar Se aaa essen eee ote pa aaa ee eee re ae Oe ‘colts tas tl oui oct ipa | denne dnscs oer ies veces ue cel waco va Oates aes es opener areren ume mere teas ocr rn Cece re Sesion agt sre ae | ‘pp, which i peoporinal to the cuftent athe cel i Te ed on sripchat a bya computer for dala analysand pre Senition \ 475 Chapier 19 Volmmetry Figure 12-0 Figure ie of mercury. As shown in Figure 19-6, the rags of potent hat canbe Shed with hese electrodes Sn aqueous solions vanes and depends ot only upon elesrode materia x soup he compostion ofthese ton in nich is immesed. General, te vouive tent Lvtatons trocauedby the lage cet that elope ote oxi? tive moka oyasn Te negates art rom the ection of penguin pcnsncineenes Wife ge Bydnpes: Nate es wlaely rye wpe roe chn Swims YS tlztel wittmercury seeUodes oving Joe heh cremate of "yrogen on thi etal rer) microcode ave been widely employed in voltammetry {or several reasons. One is the rlvey large negative potent ange Jiu deserbed Purhemor, area mee ac i ea formed Simply proocing a ew dp. ln addon, many metal ons ar eversby ‘ retest amalgams at he trace of erry cece, wh snp fe the chemisty Mercury microletodes tke several fom Te blest ofthese is merry Rim sectode formed by elstodeostion of the meal onto dik lcrode, sich st that shown i Fgwe 1930 pure 19-Soitsates hantne err dro etrnet MDE. The lecroe, wich is swim commercial sores co of ery fin eaplary tbe connected to» mercy comanag servo, The tet fred out ofthe cpa by a pion arangemest ven 8 ¢ ‘Some commos per of mone. ‘rode a) a Ceres) 9 Imerery hanging cestode (Gs crognmg mecy eect: (ete mercy doping ‘roe Bese om aac Soe aewie ear ae eee tae easy 476 Chapier 18 Votammety (omer oepar n parginty, Figen t-7 Liars vtammogram br the Fedicton af hypthetel ees ‘slcrometer screw. The micrometer permite formation of drops having ‘uefce area that are eproducibs to 3% or bee. Figure 19-3e shows 2 typical dropping mercury elecrode ‘DME, which was used in near all early po arographic experiments, Icons ‘roughly 10cm ofa fe expr tubing 0.08 mm) through ich Inercury is forced by a column of mercury of perhaps Demin beh. The ameter ofthe eapilay i sch that anew drop forms and beaks oi the ‘aplary every 2106s. The siamete of he drop is 0.3 to Ian and is Highly repeoducible. tn some apictons, the drape i conzalled by mechanical knocker that dodges the drop ata Red time fer begine 1 form. Figure 19-84 shows acommercily avaiable mercury letrode, which ‘an be operated as a dropping mercury eletode ora hanging drop elec. ode, The merry is contained ina platiesined reservoir about 13cm sbove the upper end ofthe capillary. A compression spi forces the foyurethane-iped plunger sghnst the ead ofthe eapliry, thus pe ‘eling a ow of mercury. This plunger i ited upon activation of Tie Solenoid bya sana fom the cont stem. The capillary is much ger Ja ameter (18mm tam be typical om “As el the fmt a the drop i exiemely rapid. After 3,100 oF 290 ma, the valve closed, leaving fllszed drop in place unl itis dislodged by 2 mechanical ‘noc hati bult imo the electrode suport block. Thi stm ha the advantage that the fllsized drop forms quickly and cureat mensore: ‘ents can be delved until the surface area is sale and conta. This rocedute largely climates the large curentfacteations that ree ‘huntered withthe clases! dropping electrode, 198-8 Voltammograms iute 19-7 iustates the appearance of atypia linewrscenvatamo- tam fran electlysisinvalving the redeton ofan analyte spices Ato [Brea product Pat a mercury fm mierotetrode. Her, the miracles trode is assumed tobe coancied 1a the neplive terminal of fe hineat- veer & 198 Linesr-Scan Volarmetyy 479 Scan generator 0 that the aplied potential are given a negative sign as Shows. By convention, eathodie cuments are always treed bein posive:wharea aS curents are Ea negative pn TWIG. {eial experiment, the slaion is about 10" M fa A; ODM in Pood 1.1 Min KCi, which serves asthe supporting electrolyte, The hall foe tion a the miroslesirede ithe reverb reocion Atma? BY -026V a9) For convenience, we have eepecied the charges on A and P and sso assumed thatthe standard poental forthe half reaction is 0.26 V. Ttansport processes. Limiingcurens are geerallyarelly propetional [e reactat concentration. Ths, we may write My = hey where cis he aay concnration and is constant, Quanitative lnearscan vitameety i tased upon ths relionsip. The potential at which the ciret egal tone hal he ing 1h une pce ra sce cae sealed the ha-vate teal and piven the sybl Eye me cutow eo ou ava olen ilssy ltd fo the and petal ort" = ‘eatton bu usally no seal of al9are penal se some {ines uel or enfin ef he component of saution Tnorder to ob reproducde lining Coren pi ocesary tht ether) the saluton or he micoleode bn cons a feprovible motion of ©) tt «doping Stade, vch ssa. mere eletrove, be enol Lincarssan volume in whch th Sluion orth elec uods not ion ces edn vlan) ‘mers. Votumunety that uoys sopping Cee bie pate) ‘Faplty. We shall consider both types. ‘g 198-4 Hydrodynamic Voltammetry Hydrodynamic voltammetry is performed in several ways, One method involves sing tie solution vigorously while isn contact with fied iicroletroe. Alternatively, te mirolectrde ls uated ata constant igh speed in the solution, thus >roviding te sing action il another way uf carving ou Byareaytame voltsmmetry voles cnsng eens Iyte solution to ow trough a tbe in which the microecroge. ‘mouated. The last technique isbetoming widely wed for detesting ox Alzable o educileanlyes as they exit from a quid chromatographic caluma (Seton 28C-6) ‘As described in Section 18A-2, during an electrolysis, reactants car- snp seein ae "ed tothe surface of an eecroe by tvee mechanisms migration under on miro cons ‘he influence of an electric Belt, convection resling fom siting oF 480 Chapter 19 Votlammety vibntion, and diffesion de to concentration diferences between he lof iquid at he eleciede surface andthe bulk ofthe soltion tn slam ‘nery, every efor is made to minimize the effec of avgrtion By i ‘Tegan excess ofa native supporting lecvoyte, When the cones itaton of supporting elecrlyteexcceds that of the analyte by Sb: to Tootold, the fraction of the total curent cari y. the analite ap. prosshes zero, As reso, the rate of movemen' ofthe analyte tovard the Electrode of opposite charge becomes essetally independent of applied Corcentration Profiles at Miroelectrode Surfaces During Electroysis ‘Thesghowt this dcunsion we wil consider that the electrode reaction shown in Equation 19-1 takes pce ata mercry-coated microelectrode Inasolition of A that also consis an excess of & supporting eeetrlye ‘Well assume that th nal concentration ofA ise, while tat of Pls er and that fs nt solble inthe mercury, We lea assure ta the fedtcton rection frp and revere 0 thatthe concetrtons of A ndP inthe of solution immediately adjacent tothe letrde is given Stasy instant by the Nerast equation Thi, Et = Bt = og F bu (19-2) whee Eis the poteatal between the microelectrode andthe reference ‘rods and cand are the concentrations of Pan Aina thin layer of "olin atthe eleerode surface ony. ally we nsume tht because the ‘lectrde is so very small, the electrolysis, over sho psig of ime, ‘does no ale th bulk concentration of the sltion apreeaby. That ‘the concentration of Ain the blk ofthe soltion cy fs wachangd bythe slecrolysis and the concentration of Inthe bulk ofthe soluon cp ominues tobe, fr all practical purpses, 200 (ey = 0 rote for Micrcletodes in Stired Seaton. Let us consider concen traondistance profes wien a potential is applied to a plaza miroce= ‘roe immersed ina solution thats stirred vigorously. I oder o under Stan the effect of tring i is necessary to develop a picture of guid fow ptteras in such asoaion. Thre types of Now can be ded as shovn in Figure 19-8 (1) Turbulent flow. in which auld mation has no feguar patern. cesar i the bulk ofthe slion away from the ec trode. 2) As the surge fs approached, 2 anion 0 lair flow takes ‘lac. laminae Row, ayers of gud sie by one another in iestion fail tothe eletrode surface, (3) At 8 cm from the surface ofthe fesrode, the at of laminar ow approaches zeros result of fction between the guid and the elestode giving a thin ier of stagnant sok tn, which is called the Ne liusion layer. 1s only within this ftagnnt layer that the concentrations of reactant aad prose very a 2 Function of distance trom the elacrode sae, Thali. tiroushout the lnm low and turbulent flow vesions, convssioamainaias ibe concen: I i —r = l wer MOSEL - a raion oats original vale an he concentration of Pat evel thas Figure 5-Bu shows two sels of concentration profiles for A and Pat tree potentials shown 36 X.Y, and Z 9 Figure 19-7 In Fire 19-9, the Solutions vided int wo repions. One makes up the bulk ofthe solution where mass Wanspor takes plas by mechanical convection brought shout bythe liver. The concentration ofA throughout hs region Is ‘The second region isthe Nernst siffsin iver, which is immediatly dhcen tothe electoerface apd haa tickness of bm Type, 5 "ARES Tom 0119 0.01 em, depending upon he licen’ of the irring land the viscosity of he gid. Within the sion ayer mas transport takes place By diusion alone stasis te case wih Unstred so ion: With the steed scluton, however, sin is limited to a narow [aver o qui and over ime cnnot extend indeitly into the schon, ‘AS a consequence, steady, difusoncoatlled cures ae realized Shortly afer application of vallge Figure 19-86 ives concentration profiles for P atthe tree potentials 1X. Yeand Z. In the Nemst dusonregon the coaceatraton of Pe teases nearly with distance fom the electrode surface and appecaches ‘Not inthe figures that t potent X, the equilibrium concentration of Agate cletode surface hs Been reed a about B05 of te original ‘ate, whe the equilibria concentration Phas iereaed By an equa lent amount Thats, eh = en ~ ch) At penta. which isthe halk wave poten, the equim concentrations ofthe twa species tthe Surtace are he Same ad equal to ex. Final, at potential Zand beyond, {he surface concentalon af A approaches zero and hal of P apronshes {he original concentration of A. eq. At pens nore negative than Z, essentially all A Tons entering the surface layer are instantaneously re- (deed to P. The Pfrmed in this way rapidly di uss into the bulk of he ae 198. Uneersean votsmmety Baquert ues continuo saber 481 Do 482 Chepler 19 Vottammetry cocina ‘elution so that the concenration of Pin the srfce layer remaascon- san ato Vettammetri Currents ant supe ue ei ofthe oon er ‘Ths ensiecTen esas. determined by he mpd re ‘he current n the cectrolyss experiment we have heen considering ‘sgauuntative measure of bow fis As being brought tobe sueac athe 188 LinearScan Volammetry 48% lectrode, and is rae i proportional tothe concenraion gradient ‘jl at where #& the distance i conietes from the lctrode race Fora planar elecrods W can be shows tha the current given BF the expression 19-9) caatege stow a te ni ot where ‘fs the current in amperes, i the number of moles of electrons fajgus st Seaton em per mole of nat, F isthe fray, Avs the electrode surface area in usnay ve Er Da isthe difsion coe cient fA in ems" an eis the concen: tration of A in molem®. Note that deyristhe slope ofthe itil par off Sania the concentration profiles shown in Figure 19-9a, and hes slopes ean be cere approximated by (eq ~ eh, Thertore, Equation 19-4 reduces 4 Simoes w= EP eg A= ben 2) wy here the constant ks equal 9 FAD Equation 19-4 shows hat asc becomes smaller a a result of wager negtive sppied potential, he Carre ineeaser ntl ne trace concen tration proaches 27a which pin the curren becomes constant and independest of the applied potential. Thus, when ch — 0, the curent Becomes the liming cute} and BEADS ph EARS eg key (198) This derivations based upon an oversimplified picture of the dfsion Abigale! isomer ayer in thatthe fnterace Between the noving sd stationary layers is sme. i re» eon viewed as a sharply defined edge where ramiport by convection ceases tc nce he acs sha _and transport by difision begins. Neverthles, this simpliied model gr" Sesrodesaon ws provides areasorable approximation of te relationship betwen crent ‘Ind the variables that fect the euran. ‘CurrentVoltage Relationships for Reversible Reactions ‘In order to devlep an equation fo the sigmoidal curve shown in Figure 19-7, we subi Equation 19-4 from Equation 19-3 and reaange (0 bin ¢ 09-6) ‘he surface concentration of P can also be expressed in ems ofthe curent by employing relationship sir to Eqition 19-4 Tha, BEAD a Petey et) oy a 484 Chapter 19 Votammety | | b | Figue 19-10 ‘et mitre Hilwave pe ts ier ty 01 incre 4 and teat incane & where the minus sgn results frm the negative slope of the concestration profile fr P. Note that Dp is aw the fusion coefficient of P. Bul we fave said eae tat threughos the elects the concentration of P Approaches zero in the bulk fe Solution and, therefore, when cy = 1.0 P= WFAD eh = hich where ky = mADr/4.Rearanging gives b= ity (0) Substituting Equations 19-6 aed 19-8 into Equation 19-2 yeks, ster earrangemeat 20892 ka 90892, Et = Bi ~ SOE yg Ht When i= i2, the third term o the right side of his eauation becomes qual o 227, and, by definition, Ea isthe hal-wave potential. That is, ~ Ee (19-10) ‘Substiuting this expression int» Equation 19-9 pves an expression for the voltammogram i Figure 19-7. That 00592 Ent © Big ~ 29g aon (nen, the aioe in Equation 19-10 is nearly unity, so that We may write forthe species A Ea ® Eh Ea 19-12) CCurrentiVottage Relationships for trversble Resctions Many volammetric electrode proceses, paniculaly thse asocited with organi systems, are reversible, Which leads fo draen-ot and lest Wwelldefned waves. The quantitative description of such waves requires 4a adtitonal term (volving the aclvation energy of the reaction) in Equation 19-11 to account forthe Kinetics ofthe electode process, AP though half-wave potentials for irreversible reactions ordinal show some dependence upon concentration, ifsioncurtents remain nearly felted toconcentration: such processes are, therefore, ely adapted to ‘quantitative analy, : Vottammograms for Mixtures of Reactants Ordinarily. the reactants of a mixture wil behave independently of.ane another at merolecrode:a voltammogram fora mixture ths imply 198 Linesr-Sean Vottammety 485 = a sce te ° {Guive A: anole wave fr 3 so ea Scone pane erent Saar ee eros ss coe ee ao ao sess ‘he summation ofthe waves fr the individual components. Figure 19-10 Shows the voltammograms fora pir of two-component minus. The Ina potentials of the wo reactants derby about .1V in curve A and by about 0.2 V in curve 8. Clearly a single volummogram may Permit the quunitative determination of vo ot more speci, Suesese ‘epends upon the existence of sulicientdiferencebeiween succeeding Falfvave penal o permit evaluation oinvdualdifusion cures. ‘Approximately 0.2 Vis equred ifthe more reducible species undergoes 8 Voumme hava pass ms ‘orletron reduction; minimum of about 0.3 Vt neoded the frst suprucsoy 80S mane reduction Isa one-electron process sin ra ‘Anodic and Mixed Anodic/Cathodle Voltemmograms ‘Anodic waves as wellas cathode waver are encountered in voltammetry, ‘An example ofan anodic wave sisted in curve a of Figure 1-1 where the electrode reaction involves the oxidation of iol) to roll inthe presence of citrate ion. ling curent fs obtained at about +FOL1 Ve whichis de to the halreacton Fe" a Fe te [A the pote is made more negative, a decreas nthe ano carent ‘occur: at about “0.02 V. the cient Becomes sero because the oniation fron) fon has exased, Curve C represents the volummogram for olton of ron) inthe same medium, Here, a cathodic wave resul trom reduction of the irom tothe divalent wate. The bale wave potenti Hemtcal with thal forthe anodic wave, indeating hat the oxidation anredcton ofthe two iron species are pererily reversible a the microletrode - Curve Bs the voltammogram ofan equimolar mixture of rot) and fron). The portion of the curve below the zero-current oe core sponds tothe oxidation ofthe fol) this eatin ceases tan applied potential equal othe alfwave pote. The opper potion ofthe curve ‘Se othe redaction of won a 486 Chapter 19. Vottammetyy gre 2 foronygewce 01M KCL ‘oxygen Waves is realy reduced at the dropping mercury elesroe: veour sation sarated ith sr exhib two dstint waves tbe “table to this element see Figure 19-12). The st results fom the ede ton or oxygun 10 hydrogen peroxide, The second corresponds to the reduction of the molecule to give wits, AS would be expected from Stoichiometric considerations, the wave forthe fluction to water is twice as large a5 the wave forthe Formation of hydogenperode offer 4 convenion and wiely used ved oxygen in soluions. However the ‘presonce of oxyacnoflea interferes wath the aceurste determination of ‘other species, Thus, oxygen removals odiarity theft stp in ampero- merc procedures. Deaeration ofthe slut for several minute with incr gas (sparging) accomplishes this ends 4 steam ofthe sme gas, ‘sual nitrogen, fs passed over the surface during analysis (0 prevent reabsorption of oxygen ‘Applications of Hydrodynamic Vollammetty Curent the most important uses of hydrodynaric voltammetry AS glucose, lactose. and sucror; 3) deiecion of eid pons in coo. meric and volumetric rations; fundameatal sues of electrochemi- al processes. ‘Voltammetic Detectors in Chromatography and Flw-Injetion Analy- ss, Hydrodynamic voltammetry is becoming widely used for detection ‘nd determination of oxtizabe or reducible compounds oo that have ‘een separated by nig performance qué chromatography (chapter 78) ‘or by flow-njection metheds (Section 22C). In these sppicatons 3 thin 198 Unese-Scan Votammety 487 Fane 19-14 ing eetroactive species cits layer cell suc as that shown in Figure 19-13 used The working elc- two in these cells is typically imbedded ia the wall fs insulating block that is separtd from 2 counter electrode by athia spacer a shown, The vole of schacelstypaly 0.101 a. Apo coreazonig © the limiting curen reaion fr anaes appled betwen the me assy carbon working electrode and a siver/slver chloride reference ‘lecrode that is Tocated downstream from the detector. In this type of| ‘pplication, detection limits a low as 10° to. 10- Mf analyte are ‘bined. This aplication of hydrodynamic votammery is considered further in Secon 28¢-6. ‘Volumetric Sensors. A number of voltammerc systems are produced commercially or the determination of specie species that are of interest in industry and researc. These devices are sometimes eile letroses butare in at complete voltammetric cls and ae beter refered fo a8 Sensors. Two af hese devices are described here. ‘Sonvenientmetods for making such messrements withthe Clark _2agzensequr, wich was patel by LC Clk in 986K sche. “Ge Gare oxygen star is shown In Fgue: Deis the eh O. Hoo ml arb 488 Chapler 19 Volimvretry Fur 18-8 eal cated clini, Surounding te lowed of is TeGartvetammarcongen uta Sng ape ser and Tie slat end Cee mas matte ose mums ie scope at Ss » baled Pkt) ‘Sitnn pam S/S A i os one on ne ant semaine Roni of Toon or retyte fed mnie -Faronran she ibe By av’ fig The tines of he ere ey ‘Button btveenincethole and te memtran wapproxisy 1 "When the oxygen senso Is nmersc in «owing or sired soliton of tne analve, oxygen sfc through the membrane ino the hin yer of ‘lecrlyte immediately adjacent to the disk cathode, where it dises to the clecrode ands immediatly reduced to wate. In conta 10a normal hydrodyeamic electrode, (wo difsion processes are invlvec—one Uivough the membrane an the other through the solution between the ‘membrane andthe electrode surface. (nore for a steady-state condition to be reached in a reasonable period (0 0 205), the thickness ofthe ‘membrane an the eecolyie fim must be 20 jm or less. Under these ndions, iis the rate of equation of oxygen transfer across the Imembrane shat determines the rte at whic stedy slate currents are meheved. ’A nur of eozyme-based vollammetic sensor are offeed commer- cialy. An example fs a usove sensor ta widely used in cimeal Iaborstore for he roi eTemiaton of lucose in loo serum sar FA pata Newentame | Pee, Tht dovce ssn in constrcton tthe oxygen senor shown in GL, Patgamare | rgure 19-14, The membrane inthis cas smote complex and consists of Ba remlicie, vee ayers, The outer ayer is a pycarbonte fl ths permeable to lcoce but impermeable oproeins and otberconstiuensetood. The Imi ayer an immobilized enzyie ere, glucose oxidase. The inner [lye seallose acetate membrane, which fe pormesble to small mle cles, sich ae hydrogen peroxide. When this device is immersed in @ [ecose containing slution, glucose difses through the outer membrane foto the immobiized enzyme, where the follwing ease reaction elucose + Os HyOs + laconic seit “Thehydrogen peroxide then difses through he nner yer of membrane and tothe elesrode surface, where ionized to give oxygen. Thats, 10, +2 0H" #20) + HO +26 ' “The eng urna del poporioal othe gcse cetent of he je slain evs tor tenors re aval ht re Bed won the oti merc manremen sf yap proxi predectyemyratic ote net ther specie of nal eres These anys cde sco, leone ancl and Leta, Ofcouse-a fre etyae eed foreach pce AmperometicTrtions. Hydrodyaaic valtammetry can te employed toestimate the equivalence pon of trations rovidedat leat one ofthe se patcpams or products fe reaction involved oxidize or educed at {aicrclectrode. Here, the curen at some Oe potent nthe ting ue region s measured ws func Fi oda nce eo he equals pe ag ines “Sale slops th end pins eabata by enrapoatan intersetion, “Amperometic tiation curves typically take one ofthe forms showa ia Figure 19-15. The curve in Figure [9-15 represents tation in whi the analyte reacts st the electrode while the reagent does not. Figure 1B-15b typical! of tration n which the reagent reacts a the miro

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